Background of the Invention
1. Field of the Invention
[0001] The invention relates to a process for the production of decorative coatings on substrates
using backing films provided with an uncured or only partially cured coating.
2. Description of Related Art
[0002] Backing films coated on one side with an uncured or only partially cured coating
composition are known from WO 03/013739 and WO 03/092912. These coated backing films
are used for the repair of damaged coatings on substrate surfaces, wherein the coating
layer is transferred onto the substrate and cured. As a result, only the cured coating
layer remains on the substrate, but not the backing film, which is removed before
or after completion of curing. However, the prior art does not teach the application
of special decorative patterns on substrates.
[0003] Processes are also known in which coated films are applied for decorative purposes
onto substrates, for example, vehicle bodies. Such processes are described, for example,
in WO 00/08094, WO 00/63015, EP 251546 and EP 361351. In general, the film is laminated
onto the substrate, where it remains.
[0004] There is accordingly a requirement for coating processes for the decorative coating
of substrates using coated backing films, with which even complicated decorative patterns
may be produced on the substrate surfaces concerned.
Summary of the Invention
[0005] The invention relates to a process for the production of decorative coatings, comprising
the following steps:
A) providing a substrate to be coated and a backing film coated on one side with an
uncured or only partially cured coating of a coating composition curable by means
of high-energy radiation,
B) forming zones on the backing film which are opaque to high-energy radiation and
correspond to the negative image of a desired pattern or decoration,
C) applying the coated side of the backing film having the uncured or only partially
cured coating of a coating composition curable by means of high-energy radiation onto
a substrate surface,
D) curing the coating applied by the backing film by irradiation with high-energy
radiation through the backing film,
E) removing the backing film from the coating which remains on the substrate and
F) removing any un-irradiated and thus uncured parts of the coating remaining on the
substrate to obtain the desired pattern or decoration,
wherein the zones on the backing film which are opaque to high-energy radiation and
correspond to the negative image of a desired pattern or decoration are produced before
or after application of the coated backing film onto the substrate surface.
Detailed Description of the Embodiments
[0006] If the zones which are opaque to high-energy radiation are produced before application
of the coated backing film onto the substrate surface, this may in turn proceed before
or after the backing film is coated with the coating composition curable by means
of high-energy radiation. In other words, steps A), B) and C) need not necessarily
be performed in succession; depending on how the process is performed, a modified
sequence is also possible.
[0007] The high-energy radiation used in particular comprises ultraviolet (UV) or electron
beam radiation. However, for simplicity's sake, only UV radiation will be mentioned
below.
[0008] The substrates provided in step A) of the process according to the invention may
comprise substrates made from any desired coatable materials, for example, metal,
plastics, wood or glass. The substrates may be uncoated or have a single layer or
multi-layer prior coating, for example, a paint finish. The substrates to be coated
may, for example, comprise automotive bodies, body parts or body fittings, furniture,
machinery or other industrial goods.
[0009] The individual steps of the method according to the invention are explained in greater
detail below.
[0010] Step A) of the process according to the invention comprises providing a backing film
coated on one side with an uncured or only partially cured coating layer of a coating
composition curable by means of high energy radiation. The backing film comprises
coloured or colourless, in particular transparent, films made from any desired, in
particular thermoplastic plastics which must meet certain requirements with regard
to UV transmittance and heat resistance. The films must transmit UV radiation and
be resistant to the temperatures which occur with UV radiation. The films must also
be resistant to the temperatures, optionally, required for softening the applied coating
layer. Suitable film materials are, for example, polyolefins, such as polyethylene,
polypropylene, polyurethane, pblyamide and polyesters, such as polyethylene terephthalate
and polybutylene terephthalate. Films may also consist of polymer blends and may also,
optionally, be surface-treated.
[0011] The thickness of the films may, for example, be between 10 and 1000 µm, preferably,
between 10 and 500 µm, particularly preferably between 20 and 250 µm and is determined
by practical considerations of processability. The films selected should preferably
be those which are resilient and extensible and cling effectively to the substrate
by electrostatic forces.
[0012] The backing films are coated on one side with coating compositions curable by means
of UV radiation which assume liquid, paste or melt form. The coating compositions
may be aqueous, diluted with solvents or contain neither solvents nor water. The coating
compositions curable by irradiation with UV radiation are cationically and/or free-radically
curable coating compositions known to the person skilled in the art. Free-radically
curable coating compositions are preferred.
[0013] Cationically curable coating compositions to be applied onto the backing film in
the process according to the invention contain one or more cationically polymerisable
binders. These may comprise the conventional binders known to the person skilled in
the art, such as, for example, polyfunctional epoxy oligomers containing more than
two epoxy groups per molecule. These comprise, for example, polyalkylene glycol diglycidyl
ethers, hydrogenated bisphenol A glycidyl ethers, epoxyurethane resins, glycerol triglycidyl
ether, diglycidyl hexahydrophthalate, diglycidyl esters of dimer acids, epoxidised
derivatives of (methyl)cyclohexene, such as, for example, 3,4-epoxycyclohexylmethyl
(3,4-epoxycyclohexane) carboxylate or epoxidised polybutadiene. The number average
molar mass of the polyepoxy compounds is preferably below 10,000 g/mol. Reactive diluents,
such as, for example, cyclohexene oxide, butene oxide, butanediol diglycidyl ether
or hexanediol diglycidyl ether, may also be used.
[0014] The cationically curable coating compositions may contain one or more photoinitiators.
Photoinitiators which may be used are onium salts, such as, for example, diazonium
salts and sulfonium salts.
[0015] Free-radically curable coating compositions which are preferably to be applied onto
the backing film in the process according to the invention contain one or more binders
with free-radically polymerisable olefinic double bonds. Suitable binders with free-radically
polymerisable olefinic double bonds which may be considered are, for example, any
binders known to the person skilled in the art which can be crosslinked by free-radical
polymerisation. These binders are prepolymers, such as polymers and oligomers containing,
per molecule, one or more, preferably, on average 2 to 20, particularly preferably,
3-10 free-radically polymerisable olefinic double bonds. The polymerisable double
bonds may, for example, be present in the form of (meth)acryloyl, vinyl, allyl, maleinate
and/or fumarate groups. The free-radically polymerisable double bonds are particularly
preferably present in the form of (meth)acryloyl groups.
[0016] Both here and below, (meth)acryloyl or (meth)acrylic are intended to mean acryloyl
and/or methacryloyl or acrylic and/or methacrylic.
[0017] Examples of prepolymers or oligomers include (meth)acryloyl-functional poly(meth)acrylates,
polyurethane (meth)acrylates, polyester (meth)acrylates, unsaturated polyesters, polyether
(meth)acrylates, silicone (meth)acrylates, epoxy (meth)acrylates, amino (meth)acrylates
and melamine (meth)acrylates. The number average molar mass Mn of these compounds
may, for example, be from 500 to 10,000 g/mol, preferably from 500 to 5000 g/mol.
The binders may be used individually or as a mixture. (Meth)acryloyl-functional poly(meth)acrylates
and/or polyurethane (meth)acrylates are preferably used.
[0018] The prepolymers may be used in combination with reactive diluents, i.e., free-radically
polymerisable low molecular weight compounds with a molar mass of below 500 g/mol.
The reactive diluents may be mono-, di-or polyunsaturated. Examples of monounsaturated
reactive diluents are (meth)acrylic acid and the esters thereof, maleic acid and the
semi-esters thereof, vinyl acetate, vinyl ether, substituted vinyl ureas, styrene,
vinyltoluene. Examples of diunsaturated reactive diluents are di(meth)acrylates such
as alkylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol
di(meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, divinylbenzene, dipropylene
glycol di(meth)acrylate, hexanediol di(meth)acrylate. Examples of polyunsaturated
reactive diluents are glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate,
pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate. The reactive
diluents may be used alone or in mixture.
[0019] Preferred free-radically curable coating compositions may contain one or more photoinitiators,
for example, in quantities of 0.1 to 5 wt.%, preferably of 0.5 to 3 wt.%, relative
to the sum of free-radically polymerisable prepolymers, reactive diluents and photoinitiators.
Examples of photoinitiators are benzoin and derivatives thereof, acetophenone and
derivatives thereof, for example 2,2-diacetoxyacetophenone, benzophenone and derivatives
thereof, thioxanthone and derivatives thereof, anthraquinone, 1-benzoylcyclohexanol,
organophosphorus compounds, such as for example acyl phosphine oxides. The photoinitiators
may be used individually or in combination.
[0020] The coating compositions, which may be used in the process according to the invention
for coating the backing film, preferably comprise coloured coating compositions. The
coating compositions may be pigmented with colour-imparting and/or special effect-imparting
pigments. They may, however, optionally contain transparent pigments and/or soluble
dyes in addition to the colour-imparting and/or special effect-imparting pigments.
Suitable colour-imparting pigments are any conventional coating pigments of an organic
or inorganic nature. Examples of inorganic or organic colour-impaiting pigments are
titanium dioxide, micronised titanium dioxide, iron oxide pigments, carbon black,
azo pigments, phthalocyanine pigments, quinacridone or pyrrolopyrrole pigments. Examples
of special effect-imparting pigments are metal pigments, for example made from aluminum
or copper; interference pigments, such as, for example, metal oxide coated metal pigments,
titanium dioxide coated mica. The coating compositions may also contain fillers. Examples
of usable fillers are silica, aluminium silicate, barium sulfate, calcium carbonate
and talcum.
[0021] The coating compositions may also contain conventional coating additives. Examples
of conventional coating additives include levelling agents, rheological agents, such
as highly dispersed silica or polymeric urea compounds, thickeners, for example, based
on partially crosslinked, carboxy-functional polymers or on polyurethanes, defoamers,
wetting agents, anticratering agents, catalysts, antioxidants and light stabilisers
based on HALS (hindered amine light stabilizer) products and/or UV absorbers. The
additives are used in conventional amounts known to the person skilled in the art.
[0022] The coating compositions may contain water and/or organic solvents. The latter comprise
conventional organic coating solvents known to the person skilled in the art.
[0023] The coating compositions curable by means of UV radiation may be applied onto the
backing film by conventional methods, for example by brushing, roller coating, casting,
knife coating, spraying or electrostatic spraying or by screen printing. The coating
composition may be applied as a melt or in the liquid phase, for example as a solution.
The coating compositions may, for example, be knife coated as a solution. In the subsequent
drying process, the solvent is allowed to evaporate, optionally with gentle heating.
The dried, uncrosslinked coating should advantageously be slightly tacky at room temperature
in order to ensure good adhesion onto the substrate to be decorated. The coating may
either be intrinsically tacky due to specially formulated binders or tackiness may
be achieved by slight partial crosslinking/gelling of the dried coating, for example,
by heating and/or by UV irradiation. However, the coating must not in any event cure
completely at this stage. The coating compositions curable by means of UV radiation
are generally applied in dry film thicknesses of 1 to 100 µm, preferably of 5 to 60
µm.
[0024] In order to facilitate subsequent removal of the backing film from the substrate
to be decorated, it may be advantageous to leave at least one edge zone of the backing
film uncoated. It may also be advantageous to provide a special finish on the side
of the backing film which is to be coated, for example, a release coating, or to use
special surface-treated films, for example, films surface-modified with silicate layers,
in order, on removal of the backing film, to facilitate detachment from the coating
which is fixed to the substrate to be decorated.
[0025] It may also be advantageous to provide the coated backing film with a temporary protective
film to provide protection. The protective film may here be present only on the coated
side of the backing film, but it may also be applied onto both sides and completely
enclose the entire coated backing film. In order to protect the coating on the backing
film from premature polymerisation brought about by UV radiation, a transparent or
coloured, for example, black, UV-opaque material may advantageously be used for the
protective film. A black polyethylene protective film may, for example, be used. In
order to facilitate detachment of the protective film, it too may also, as described
above, be provided with non-stick properties. The coating may be protected by using
a release paper instead of a protective film.
[0026] The backing films coated on one side and optionally, provided with a protective film,
protective wrapping or release paper, may be prefabricated and stored in the most
varied shapes and sizes, for example in sizes of 5 cm
2 to 1 m
2. Depending on the object to be decorated, larger films are, of course, also possible.
The films may also be stored as a reel of continuous film.
[0027] In step B) of the process according to the invention, zones opaque to UV radiation
are produced on the UV-transmitting backing film in order to avoid curing at these
points on subsequent irradiation. The zones opaque to UV radiation here correspond
to the negative image of a desired pattern or decoration or the UV radiation transmitting
zones correspond to the desired pattern or decoration which is ultimately to be produced
on the substrate surface to be decorated.
[0028] There are various possible ways of producing zones opaque to UV radiation on the
backing film. In principle, the zones opaque to UV radiation may be produced before
or after application of the backing film onto the substrate surface. Preferably, a
coating opaque to UV radiation corresponding to the negative image of a desired pattern
or decoration is applied onto an uncoated side of the backing film before the backing
film is applied onto the substrate surface. This may in turn proceed before the backing
film is coated with the UV-curable coating composition or thereafter. Coating to produce
the zones opaque to UV radiation may, for example, proceed by printing, for example
by means of screen printing, inkjet printing or laser printing. The layer applied,
for example, printed, in order to produce zones opaque to UV radiation is completely
dried or cured after application. Selection of corresponding coating compositions
is not subject to any particular restrictions with regard to the binders and the further
components. All that must be ensured is that the coating obtained in this manner does
not transmit UV radiation. This may be achieved, for example, by appropriate pigmenting.
If the zones opaque to UV radiation are produced before the backing film is coated
with the UV curable coating composition, the UV curable coating composition may be
applied onto the side of the film which comprises zones opaque to UV radiation or
onto the side of the film which does not comprise zones opaque to UV radiation. In
the former case, the image which is to be printed, for example, must be applied onto
the film not only as a negative image but also as a mirror-reversed image of the desired
pattern or decoration.
[0029] It is furthermore also possible to produce the zones opaque to UV radiation on the
uncoated side of the backing film after the backing film has been applied with its
coated side onto the substrate surface. The already applied coated backing film may
here be masked off with a UV-opaque mask or stencil in the form of the negative image
of a desired pattern or decoration. The entire mask may be UV-opaque and correspond
in its overall shape to the negative image of a desired pattern or decoration or the
mask may contain only specific UV-opaque zones in the form of the negative image of
a desired pattern or decoration.
[0030] Obviously, the size of the mask must correlate with the size of the backing film
used.
[0031] A suitable selection of correspondingly coated and printed films may, in principle,
be prefabricated and held in stock and so be quickly available for use. Alternatively,
a suitable selection of films coated on only one side and corresponding masks may
be prefabricated and held in stock.
[0032] After provision of a backing film coated on one side with a UV curable coating composition
and removal of an optionally present protective film, protective envelope or release
paper, the backing film is applied with its coated side onto the substrate surface
to be decorated in accordance with step C) of the process according to the invention.
The substrate surface to be decorated may be lightly keyed or roughened before application
of the coated backing film in order to ensure good adhesion. The film is then laminated
onto the substrate, preferably with exposure to pressure and, optionally, heat, so
fixing the coating onto the substrate to be decorated. This may, for example, be carried
out with a heatable roller, for example, a rubber roller. The coated backing film
may here be applied onto any uncoated or already coated substrate surfaces.
[0033] After application of the coated side of the coated backing film onto the substrate
surface to be decorated and the prior or subsequent production of UV-opaque zones
on one side of the backing film, the coating applied in this manner is irradiated
with UV radiation through the backing film.
[0034] The preferred source of radiation comprises UV radiation sources emitting in the
wave length range from 180 to 420 nm, in particular from 200 to 400 nm. Examples of
such UV radiation sources are optionally doped high, medium and low pressure mercury
vapour emitters, gas discharge tubes, such as, for example, low pressure xenon lamps
and UV lasers.
[0035] Apart from these continuously operating UV radiation sources, however, it is also
possible to use discontinuous UV radiation sources. These are preferably so-called
high-energy flash devices (UV flash lamps). The UV flash lamps may contain a plurality
of flash tubes, for example, quartz tubes filled with inert gas, such as xenon. The
UV flash lamps have an illuminance of, for example, at least 10 megalux, preferably,
from 10 to 80 megalux per flash discharge. The energy per flash discharge may be,
for example, 1 to 10 kJoule.
[0036] The irradiation time with UV radiation when UV flash lamps are used as the UV radiation
source may be, for example, in the range from 1 millisecond to 400 seconds, preferably,
from 4 to 160 seconds, depending on the number of flash discharges selected. The flashes
may be triggered, for example, about every 4 seconds. Curing may take place, for example,
by means of 1 to 40 successive flash discharges.
[0037] If continuous UV radiation sources are used, the irradiation time may be, for example,
in the range from a few seconds to about 5 minutes, preferably less than 5 minutes.
The distance between the UV radiation sources and the surface to be irradiated may
be, for example, 5 to 60 cm.
[0038] It may be advantageous to assist the UV radiation curing by the supply of thermal
energy.
[0039] For completeness' sake, it should be mentioned that when electron beam radiation
is used as the high-energy radiation, it is, of course, necessary to use electron
beam transmitting film materials and correspondingly, to produce electron beam-opaque
zones on the film.
[0040] After irradiation with UV radiation through the backing film, the backing film, optionally
together with the mask, is removed after the irradiation. If thermal energy was additionally
supplied, the coating is first allowed to cool before the backing film is removed.
[0041] After removal of the backing film, optionally together with the mask, a coating remains
on the substrate surface, which comprises fully cured and uncured zones. The un-irradiated
and thus uncured zones of the coating are removed. This may, for example, proceed
by rinsing with organic solvents, such as ketones, for example, acetone, alcohols,
for example, isopropanol or esters, for example butyl acetate or ethyl acetate. If
water-soluble binders have been used, rinsing may also be performed using water or
mixtures of water and water-miscible_organic solvents. If necessary, surfactants may
also be added to the solvents or mixtures used for rinsing. Once the uncured zones
of the coating have been rinsed away, the desired pattern/decoration is obtained on
the substrate surface, said pattern/decoration generally contrasting with the background
with regard to colour or special effect. If desired, the surface decorated in this
manner, in particular, the pattern or decoration produced, may be overcoated with
a final transparent coating layer to provide protection. Finally, the correspondingly
decorated substrate surface may optionally also be polished.
[0042] The process according to the invention may be used to provide decorative coating
on any desired coated or uncoated substrates, for example, in industrial and vehicle
coating and in general in any application in which substrate surfaces are to be provided
with patterns or decoration, including pictures, logos, graphics or words. In addition
to coating for purely decorative purposes, the applied pictures, logos, words etc.
may also serve to provide information and marking. Use in workshops, such as, for
example, automotive repair shops or body shops, or in do-it-yourself applications
is also possible. The particular advantage of the process according to the invention
is that it is relatively straightforwardly possible to produce exactly reproducible
patterns, pictures or logos on substrate surfaces by means of prefabricated, coated
backing films, without involving costly spray application.
[0043] The following Examples are intended to illustrate the invention in greater detail.
EXAMPLE
Production of a coated backing film
[0044] A polyurethane resin curable by means of UV radiation was first produced as follows:
369.4 parts by weight (pbw) of isophorone diisocyanate were combined with 0.6 pbw
of methylhydroquinone and 80 pbw of butyl acetate in a 2 L four-necked flask with
a stirrer, thermometer, dropping funnel and reflux condenser and heated to 80°C. A
mixture of 193 pbw of hydroxyethyl acrylate and 0.5 pbw of dibutyltin dilaurate was
added dropwise in such a manner that the reaction temperature did not rise above 100°C.
50 pbw of butyl acetate were used to rinse out the dropping funnel. The temperature
was maintained at a maximum of 100°C until an NCO-value of 10.1 was obtained. 300
pbw of a polycaprolactone triol (Capa 305 from Interox Chemicals) and 50 pbw of butyl
acetate were then added. The reaction mixture was maintained at a maximum of 100°C
until an NCO-value of <0.5 was obtained. The mixture was then diluted with 69.6 pbw
of butyl acetate. A colourless, highly viscous resin with a solids content of 75 wt.%
(1h/150°C) and a viscosity of 10,000 mPas was obtained.
[0045] A UV curable pigmented coat was then produced from the following constituents:
80.8 wt.% of the acryloyl-functional polyurethane resin produced above
1.3 wt.% of a conventional commercial photoinitiator (Irgacure® 184, CIBA)
0.1 wt.% of a conventional commercial levelling agent (Ebecryl® 350, UCB)
0.8 wt.% of a conventional commercial UV absorbent (Tinuvin® 384, CIBA)
0.8 wt.% of a conventional commercial light stabiliser (HALS based) (Tinuvin® 292,
CIBA)
1.1. wt.% of a red pigment Paliogenmaron L 3920 BASF)
15.1 wt.% of butyl acetate.
[0046] The backing film prepared was a 20 µm thick polyester film (20 cm by 15 cm) printed
with the negative image of a logo with a carbon black containing ink, the printed
areas of the polyester film being opaque to UV radiation. The red pigmented coating
produced above was then applied onto the unprinted side of the polyester film. To
this end, the coating was applied by knife coating to a dry film thickness of approximately
40 µm. The applied coating layer was dried for 10 minutes at 60°C to evaporate the
solvent. A slightly tacky, no longer flowable surface was obtained.
Application of the coated backing film
[0047] The coated film prepared above was laid with its coated side onto a motor vehicle
bonnet (hood) which was to be decorated. The bonnet had a typical automotive multi-layer
coating comprising electrodeposited primer, filler coat, base coat and clear coat.
The coating film was then heated through the film with an IR radiation emitter to
approximately 80°C and laminated without bubbles onto the blemished area under gentle
pressure. The still warm and liquid coating material was then irradiated through the
film by means of 15 flashes from a UV flash lamp (3000 Ws) at a distance of 20 cm.
The flashes were triggered every 4 seconds. After irradiation, the film was peeled
off. The uncured zones of the coating remaining on the substrate were then rinsed
away with isopropanol. A perfectly formed red logo of the desired kind was left behind
on the surface.
1. A process for the production of decorative coatings on substrate surfaces comprising
the following steps:
A) providing a substrate to be coated and a backing film coated on one side with an
uncured or only partially cured coating of a coating composition curable by means
of high-energy radiation,
B) forming zones on the backing film which are opaque to high-energy radiation and
correspond to the negative image of a desired pattern or decoration,
C) applying the coated side of the backing film having the uncured or only partially
cured coating of a coating composition curable by means of high-energy radiation with
the coated side thereof onto a substrate surface,
D) curing the coating applied by the backing film by irradiation with high-energy
radiation through the backing film,
E) removing the backing film from the coating which remains on the substrate, and
F) removing any un-irradiated and uncured parts of the coating remaining on the substrate
to obtain a desired pattern or decoration,
wherein the zones on the backing film which are opaque to high-energy radiation and
correspond to the negative image of a desired pattern or decoration are produced before
or after application of the coated backing film onto the substrate surface.
2. A process according to claim 1, wherein the zones opaque to high-energy radiation
are produced before application of the coated backing film onto the substrate surface.
3. A process according to claim 1, wherein the zones opaque to high-energy radiation
are produced before the backing film is coated with the coating composition curable
by means of high-energy radiation.
4. A process according to claim 3, wherein the coating composition curable by means of
high-energy radiation is applied onto the side of the backing film which does not
comprise the zones opaque to high-energy radiation.
5. A process according to claim 1, wherein the zones opaque to high-energy radiation
are produced after application of the backing film onto the substrate surface by masking
off the backing film with an at least partially UV-opaque mask or stencil.
6. A process according to claim 1, wherein the zones opaque to high-energy radiation
are produced by printing UV-opaque coatings onto one side of the backing film.
7. A process according to claim 1, wherein the uncured or only partially cured coating
layer applied onto the backing film comprises a coating layer with a tacky surface.
8. A process according to claim 1, wherein the coating composition curable by means of
high energy radiation comprises a coating composition with free-radically polymerisable
binders, cationically polymerizable binders or mixtures thereof.
9. A process according to claim 1, wherein irradiation proceeds with UV radiation of
the wavelength range of 180-400 nm.
10. A process according to claim 1, wherein removal of the un-irradiated and uncured portions
of the coating remaining on the substrate proceeds by rinsing with organic solvents,
water or mixtures of organic solvents and water.
11. A process according to claim 1 for providing a decorative coating on coated or uncoated
substrate surfaces.
12. A process according to claim 1, wherein the substrate surfaces to be decorated comprise
vehicle coating or industrial coatings.